Inhibiting foam



United States Patent Office 3,313,736 Patented Apr. 11, 1967 This application is a division of application Ser. No. 47,387, filed on Aug. 4, 1960, now abandoned, and is copending with application Ser. No. 458,373, filed on May 24, 1965, now abandoned, as a division of said application Ser. No. 458,373, and is also a continuation of application Ser. No. 115,881, filed on June 9, 1961, now abandoned, and is copending with each of the following applications:

Serial Filing Date Title Oct. 24, 1965 Fuel Composition. June 9, 1961 Process of Preventing Scale, granted as Patent No. 3,251,778 on May 17,

Preventing Corrosion, granted as U.S.

Patent No. 3,262,791 on July 26, 1966. Process of Breaking Emulsions, now

abandoned. Lubricating Composition. Flotation Process, now abandoned. Drilling Fluids, now abandoned. Treatment of Oil Wells, now abandoned. Anti-Stripping Agents, granted as 11.8. Patent No. 3,259,513 on July 5, 1966.

115, 878 115, 882 115, ass 115, 884 308, 063

Oct. 24, 1965 9,1961 9,1961 June 9,1961 June 9,1961 Sept. 11,1963

June

June June This invention relates to polyalkyleneimines and to derivatives thereof. More particularly, this invention relates to polyethyleneimine and to polyethyleneimine derivatives containing various groups, such as the oxyalkylated acylated, alkylated, carbonylated, olefinated, etc., derivatives thereof, prepared by introducing such groups individually, alternately, in combination, etc., including for example, derivatives prepared by varying the order of adding such groups, by increasing the number and order of adding such groups, and the like.

This invention also relates to methods of using these products, which have an unexpectedly broad spectrum of uses, for example, as demulsifiers for water-in-oil emulsions; as demulsifiers for oil-in-water emulsions; as corrosion inhibitors; as fuel oil additives for gasoline, diesel fuel, jet fuel, and the like; as lubricating oil additives; as scale preventatives; as chelating agents or to form chelates which are themselves useful, for example, as antioxidants, gasoline stabilizers, fungicides, etc.; as flotation agents, for example, as flotation collection agents; as asphalt additives or anti-stripping agents for asphalt-mineral aggregate compositions; as additives for compositions useful in acidizing calcareous stratas of oil wells; as additives for treating water used in the secondary recovery of oil and in disposal wells; as additives used in treating oil-well strata in primary oil recovery to enhance the flow of oil; as emulsifiers for both oil-in-water and Water-in-oil emulsions; as additives for slushing oils; as additives for cutting oils; as additives for oil to prevent emulsification during transport; as additives for drilling muds; as agents useful in removing mud sheaths from newly drilled Wells; as dehazing or .fog-inhibiting agents for fuels; as additives for preparing sand or mineral slurries useful in treating oil wells to enhance the recovery of oil; as agents for producing polymeric emulsions useful in preparing water-vapor impermeable paperboard; as agents in parafiin solvents; as agents in preparing thickened silica aerogel lubricants; as gasoline additives to remove copper therefrom; as deicing and antistalling agents for gasoline; as antiseptic, preservative, bactericidal, bacteriostatic, germicidal, fungicidal agents; as agents for the textile industry, for example, as mercerizing assistants, as wetting agents, as rewetting agents, as dispersing agents, as detergents, as penetrating agents, as softening agents, as dyeing assistants, as anti-static agents, and the like; as additives for rubber latices; as entraining agents for concrete and cements; as antistatic agents for rugs, floors, upholstery, plastic and wax polishes, textiles, etc; as detergents useful in metal cleaners, in floor oils, in dry cleaning, in general cleaning, and the like; as agents usefulin leather processes such as in fiat liquoring, pickling, acid degreasing, dye fixing, and the like; as agents in metal pickling; as additives in paints for improved adhesion of primers, in preventing water-spotting in lacquer; as anti-Skinners for pigment flushing, grinding and dispersing, as antifeathering agents in ink; as agents in the preparation of wood pulp and pulp slurries, as emulsifiers for insecticidal compositions and agricultural sprays such as DDT, 2,4-D (Toxaphene), chlordane, nicotine sulfate, hexachloracyclohexane, and the like; as agents useful in building materials, for example, in the water repellent treatment of plaster, concrete, cement, roofing materials, floor sealers; as additives in bonding agents for various insulating building materials; and the like,

Polyalkyleneimine employed in this invention include high molecular Weight polyethyleneimine, i.e. polymers of ethyleneimine CH2-CH2 or substituted products thereof:

ORr-CR'z CRz-OR2 N N H etc., wherein R, R and R are hydrogen or a substituted group, for example a hydrocarbon group such as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, etc., but preferably hydrogen or alkyl.

Thus, polyethyleneimine is polymerized, substituted or an unsubstituted, 1,2-alkyleneimine. Although polyethyleneimine is the preferred embodiment, other illustrative examples include, for example,

CHI-CH3 EN CH2 1,2-propyleneirnine CH-CzHs 1,2-butyleneimine GEL-CH3 HN l 011-011, 2,3-butyleneirnine CH: HN\| CH3 CH: 1, l-dimethylethylimine CH-ClHB c-butylethyleneimine c-dodecylethyleneimine CH-C isHar c-octadecylethyleneimine A preferred class of polymerized 1,2-alkyleneimines include those derived from polymerizing RCHRCH wherein R and R are hydrogen or an alkyl radical, the latter being the same or different. Of the substituted ethyleneimines, propyleneimines are preferred.

The polyethyleneimines useful herein have molecular weights of, for example, at least 800, for example from 800 to 100,000 or higher, but preferably 20,000 to 75,000 or higher. There is no upper limit to the molecular weight of the polymer employed herein and molecular weights of 200,000, 500,000 or 1,000,000 or more can be employed.

The optimum molecular weight will depend on the particular derivative, the particular use, etc.

Although these products are generally prepared by polymerizing 1,2-alkyleneimines, they may also be prepared by other known methods, for example, by decarboxylating 2-oxazolidine as described in 2,806,839, etc.

Commercial examples of these compounds are available, for example, those sold by the Chemirad Corporation as PEI in a 50% by weight aqueous solution having a molecular weight of 3040,000. Propyleneimine is also comercially available and suitable polymers can be prepared from this material.

For convenience and simplicity, this invention will be illustrated by employing polyethyleneimine.

Polyethyleneimine is a well known polymer whose preparation from ethyleneimine is described in US. Patent 2,182,306 and elsewhere. For convenience in polymerizing and handling, the polymer is generally prepared as an aqueous solution. Water can be removed, if desired, by distilling the water therefrom or by azeotroping the water therefrom in the presence of a hydrocarbon, such as xylene, and using the solution and/or suspension obtained thereby for further reaction or use. The following polyethyleneimines of the molecular weights indicated are employed herein to illustrate this invention.

Polymer designation: Approx. mol. wgt. range Polyethyleneimine 900 800-1000 Polyethyleneimine 5,000 4000-6000 Polyethyleneimine 11,500 10,50012,500 Polyethyleneimine 20,000 18,00022,000 Polyethyleneimine 35,000 30,00040,000 Polyethyleneimine 50,000 40,00060,000 Polyethyleneimine 75,000 65,000-85,000 Polyethyleneimine 100,000 80,000125,000

Acylation A wide variety of acylating agents can be employed. Acylation is carried out under dehydrating conditions, i.e., water is removed. Any of the well-known methods of acylation can be employed. For example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., are all satisfactory.

The temperature at which reaction between the acylating agent and polyethyleneimine is effected is not too critical a factor. Since the reactions involved appear to be an amide-formation reaction and a condensation reaction, the general temperature conditions for such reactions, which are well known to those skilled in the art, are applicable.

Acylation is conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from to 280 C., but preferably at to 200 C.

The product formed on iacylation will vary with the particular conditions employed. First the salt, then the amide is formed. If, however, after forming the amide at a temperature between 140-250 C., but usually not above 200 C., one heats such products at a higher range, approximately 250-280 C., or higher, possibly up to 300 C. for a suitable period of time, for example, 1-2 hours or longer, one can in many cases recover a second mole of water for each mole of carboxylic acid group employed, the first mole of water being evolved during amidification. The product formed in such cases contains a cyclic amidine ring, such as an imidazoiine or a tetrahydropyrimidine ring. Infrared analysis is a convenient method of determining the presence of these groups.

Water is formed as a by-product of the reaction between the acylating agent and polyethyleneimine. In or der to facilitate the removal of this water, to effect a more complete reaction in accordance with the principle of LeCh-atelier, a hydrocarbon solvent which forms an azeotropic mixture with water can be added to the reaction mixture. Heating is continued with the liquid reaction mixture at the preferred reaction temperature, until the removal of water by azeotropic distillation has substantially ceased. In general, any hydrocarbon solvent which forms an azeotropic mixture with water can be used. It is preferred, however, to use an aromatic hydrocarbon solvent of the benzene series, Non-limiting examples of the preferred solvent are benzene, toluene, and xylene, The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and the reaction temperature selected. Accordingly, a sufficient amount of solvent must be used to support the azeotropic distillation, but a large excess must be avoided since the reaction temperature will be lowered thereby. Water produced by the reaction can also be removed by operating under reduced pressure. When operating with a reaction vessel equipped with a reflux condenser provided with a water takeoff trap, sufiicient reduced pres" sure can be achieved by applying a slight vacuum to the upper end of the condenser. The pressure inside the system is usually reduced to between about 50 and about 300 millimeters. If desired, the water can be removed also by distillation, while operating under relatively high temperature conditions.

The time of reaction between the acylating agent and polyethyleneimine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the water from the reaction mix ture. In practice, the reaction is continued until the formation of water has substantially ceased. In general, the time of reaction will vary between about 4 hours and about ten hours.

Although a wide variety of carboxylic acids produce excellent products, carboxylic acids having more than six carbon atoms and less than 40 carbon atoms but preferably 8-30 carbon atoms give most advantageous products. The most common examples include the detergent forming acids, i.e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturallyoccuring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources and are different in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, propionic, butyric, vleric, capronic, heptanoic, caprylic, nonanoic, capric, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosan-oic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, crot-onic, anglic, teglic, the pentenoic acids, the hexenoie acids, for example, hydrosorbic acid,

the heptenoic acids, the octenoic acids, the nonenoic acids,

the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodencenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitoleic acid, the heptadecenoic acids, the octodecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the decosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetradosenic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudoeleostearic acid. and the like.

Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hydroxy-heptanoic acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxy-myristic acids, the hydroxypentadecanoic acids, the hydroxy-palmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelardic acid, hydroxyoctadecynoic acids, for example, ricinstearolic acid, the hydroxyeicosanoic acids, for example, hydroxyarachidic acid, the'hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydrocarbic and chaumoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fencholic acids, and the like.

Examples of aromatic monocarboxylic acids are benzoic acid, substituted benzoic acids, for example, the toluic acids, the xylenic acids, alkoxy benzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed. Fatty and similar acids include those derived from various waxes, such as bees-wax, sperrnaceti, montan wax, Japan wax, coccerin and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such as from paraflin wax, petroleum 6 and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesocem'c, citraconic, glutonic, itaconic, muconic, aconitic acids, and the like,

Examples of aromatic polycarboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two carboxylic groups are himimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids are the dimeric, trimeric, and polymeric acids, for example, dilinoleic, trilinoleic, and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as acid anhydrides, esters, acid halides, glycerides, etc., can be employed in place of the free acid.

Examples of acid anhydrides are the alkenyl succinic acid anhydrides.

Any alkenyl succinic acid anhydride or the corresponding acid is utilizable for the production of the reaction products of the present invention. The general structural formulae of these compounds are:

Anhydride o R-OH-i') CH2C/ wherein R is an alkenyl radical. The alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein. However, it is preferred to use an alkenyl succinic acid anhydride reactant having between about 8 and about 18 carbon atoms per alkenyl radical. Although their use is less desirable, the alkenyl succinic acids also react, in accordance with this'invention, to produce satisfactory reaction products. It has been found, however, that their use necessitates the removal of water formed during the reaction and also often causes undesirable side reactions to occur to some extent. Nevertheless, the alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Accordingly, when the term alkenyl succinic acid anhydride, is used herein, it must be clearly understood that it embraces the alkenyl succinic acids as well as their anhydrides, and the derivatives thereof in which the olefinic double bond has been saturated as set forth hereinbefore. Non-limiting examples of the alkenyl succinic acid anhydride reactant are ethenyl succinic acid anhydrides; ethenyl succinic acid; ethyl succinic acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid; Z-methylbutenyl succinic acid anhydride; 1,2-dichloropentyl succinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized 3-methylpentenyl succinic acid anhydride; 2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenyl succinic acid; 1,2-dibromo-2-ethylbutyl succinic acid; heptenyl succinic acid anhydride; 1,2-diiodooctyl succinic acid; octenyl succinic acid anhydride; Z-methyl-heptenyl succinic acid anhydride; 4-ethylhexenyl succinic acid; 2-isopropylpentenyl succinic acid anhydride; noneyl succinic acid anhydride; 2-propylhexenyl succinic acid anhydride; decenyl succinic acid; decenyl succinic acid anhydride; 5-methyl-2-isopropylhexenyl succinic acid anhydride; 1,2-dibrorno-2-ethyloctenyl succinic acid anhydride; decyl succinic acid anhydride; undecenyl succinic acid anhydride; 1,2-dichloroundecyl succinic acid anhydride; 1,2-dichloro-undecyl succinic acid; 3-ethyl-2-t-butylpentenyl succinic acid anhydride; dodecenyl succinic acid anhydride; dodecenyl succinic acid; 2-pr0pylnonenyl succinic acid anhydride; 3- butyloctenyl succinic acid anhydride; tridecenyl succinic acid anhydride; tetradecenyl succinic acid anhydride; hexadecenyl succinic acid anhydride; sulfurized octadecenyl succinic acid; octadecyl succinic acid anhydride; 1,2-dibrom-2-methylpentadecenyl succinic acid anhydride; S-propylpentadecyl succinic acid anhydride; eicosenyl succinic acid anhydride; 1,2-dichloro-2-methylnonadecenyl succinic acid anhydride; 2-octyldodecenyl succinic acid; 1,2-diiodotetracosenyl succinic acid anhydride; hexacosenyl succinic acid; hexacosenyl succinic acid anhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are well known to those familiar with the art. The most feasible method is by the reaction of an olefin with maleic acid anhydride. Since relatively pure olefins are difficult to obtain, and when thus obtainable, are often too expensive for commercial use, alkenyl succinic acid anhydrides are usually prepared as mixtures by reacting mixtures of olefins with maleic acid anhydride. Such mixtures, as well as relatively pure anhydrides, are utilizable herein.

In summary, without any intent of limiting the scope of the invention, acylation includes amidification, the formation of the cylic amidine ring, the formation of acid imides such as might occur when anhydrides such as the alkenylsuccinic acids are reacted, i.e.

wherein P=the polyethyleneimine residue, polymers as might occur when a dicarboxylic acid is reacted intermolecularly with polyethyleneimine, cyclization as might occur when a dicarboxylic acid reacts intramolecularly with polyethyleneimine as contrasted to intermolecular reactions, etc. The reaction products may contain other substances. Accordingly, these reaction products are most accurately defined by a definition comprising a recitation of the process by which they are produced, i.e., by acylation.

The moles of acylating agent reacted with polyethyleneimine will depend on the number of acylation reactive positions contained therein as well as the number of moles of acylating agent one wishes to incorporate into the polymer. Theoretically one mole of acylating agent can be reacted per amino group on the polyethyleneimine molecule. We have advantageously reacted 120 moles of acylating agent per mole of polyethylene 900, but preferably l-l2 moles. Proportionately greater amounts of acylating agent can be employed with polyethyleneimine of higher molecular weight. Thus, with polyethyleneimine 20,000, 1-50 moles of acylating agent can be employed, and with polyethyleneimine 35,000, 1100 moles can be employed, etc. Optimum acylation will depend on the particular use.

The following examples are illustrative of the preparation of the acylated polyethyleneimine.

The following general procedure is employed in acylating. A xylene suspension of polyethyleneimine, after the removal of water, is mixed with the desired ratio of acid. Heat is then applied. After the removal of the calculated amount of water (1 to 2 equivalents per carboxylic acid group of the acid employed), heating is stopped and the azeotroping agent is evaporated under vacuum. The temperature during the reaction can vary from to 200 C. Where the formation of the cyclic amidine type structure is desired, the maximum temperature is generally l80-250 C. and more than one mole of water per carboxylic group is removed. The reaction times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example 1A The reaction is carried out in a 5 liter, 3 necked flask furnished with a stir-ring device, thermometer, phase separating trap, condenser and heating mantle to 1 mole (900 grams) of polyethylenimine 900 in an equal weight of xylene (i.e., 900 grams), 200 grams of lauric acid (1 mole) is added with stirring in about ten minutes. The reaction mixture is then heated gradually to about C. in half an hour and then held at about C. over a period of 3 hours until 19 grams (1.1 moles) of water is collected in the side of the tube. The solvent is then removed with gentle heating under reduced pressure of approximately 20 mm. The product is a dark, viscous, xylene-soluble liquid.

Example 1-A The prior example is repeated except that the final reaction temperature is maintained at 240 C. and 36 grams (2 moles) of water are removed instead of 19 grams (1.1 moles). Infrared analysis of the product in dicates the presence of a cyclic amidine ring.

The following examples of acylated polyethyleneimines are prepared in the manner of the above examples from the polyethyleneimine noted in the following table. The products obtained are dark, viscous materials.

In the examples the symbol A identifies the acylated polyethyleneimine. Thus, specifically l-A, represents acylated polyethyleneimine.

TABLE I.ACYLATE1])E PgtODUCTS OF POLYETHYL- N IMIN E Molecular Ratio Mols Weight of Ratio Mols of Water Ex. Acid Polyethylof Acid Per Removed eneimine M01 01 PE Per M01 (PE) of Acid 1A Laurie (200) 900 10:1 1.12 1-Az... do 900 8:] 1.3 900 6:1 1. 5 900 5:1 1. 1 900 4:1 1. 85 900 1:1 2. 0

5,000 5:1 1.02 5, 000 4:1 1. 6 2-A4.-. d o 5,000 1:1 2.0 3A1 Acetic (60) 11,500 10:1 1.3

TABLE ICon tinued Molecular Ratio Mols Weight of Ratio Mols of Water Ex. Acid Polyethylof Acid Per Removed eneimine Mol of PE Per M01 (PE) of Acid 3-Az.-. Acetic (G) 11,500 :1 1.8 3-113-.. do 11,500 2:1 1.1 11, 500 1 1 1. 2 11, 500 3:1 1. 6 11, 500 2 1 1. 3 11, 500 1 1 2. 0 20, 000 3: 1 1. 4 20, 000 2: 1 1. 1 20, 000 3:1 1. 5

20, 000 2: 1 2. 0 20, 000 l :1 1. 1 20, 000 1:2 2. 0 50, 000 3:1 1. 7 50, 000 2:1 1. 0 7-A d0 50,000 1:1 1.5 8-111..- Myristic (228.4)"- ,000 3:1 1.1 8-Ag.-- do 50,000 2:1 1.9 8Aa d0 50,000 1:1 1.3 9-111- Alkenyl (C12) 50, 000 6:1 1. 5

Succinic Anhy.

50, 000 l :1 1. 2 11-111. Maleic 50, 000 1 1 Anhydride (98). 11-112-. .do 50,000 0.8:1 00, 000 1:2 100, 000 2 1 1. 6 100, 000 1: l 1. 4 100, 000 1 1 1. 0 13-112.. do 100,000 1:2 2.0 14-11 Diphenolic (286) 100, 000 2:1 1. 1 I l-A2 d0 100,000 1:1 1.1

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE I-A.AOYLATED PROIIIKIIITECTS OF POLYPROPYL- ENEIM Molecular Mols of Acid Mols of Water Exam- Weight of Acid Per M01 of Removed ple Polypropyl- Polypropyl- Per M01 of eneimine eneimine Acid 15-91 500 Stearic (284)- 2:1 1.9 15-112-- 500 do 1:1 1.1 15-113. 500 Laurie (200) 1:1 0.9 16-A1 1, 000 Oleic (282) 3:1 1.0 16-11 1, 000 Palmitic (256.4)- 1:1 1. 2 Iii-A3- 1, 000 Acetic (60) 2:1 1.0 17-111- 5, 000 Stearic (284) 1:1 2. 0 17A 5,000 do 3:1 1.3 17-11 5,000 Dimeric (600) 1:1 1. 5

' (Emery Indus tries). 18-111- 10,000 Diglycolie (134) 4:1 0. 9 18-111. 10,000 Diphenolie (285) 2:1 1. 0 18-11;. 10, 000 Naphthenio (330) 1: 1 1. 0 19-11; 20, 000 Maggie Anhydride 1:1 19Az 20,000 Nonanoic (15S) 4: 1 3. 2 19A 20, 000 Oleic (282) 2:1 2. 1 20A 40, 000 Myristic (228.4) 2:1 1. 7 20Az 40,000 Oleie (282) 3:1 2.8 211-113. 40, 000 Alkenyl (C12) 1:1

Suceinic Anhydride (266).

OXYALKYLATION Polyethyleneimine can be oxyalkylated in the conventional manner, for example, by means of an alpha-beta alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, octylene oxide, a higher alkylene oxide, styrene oxide, glycide, methylglycide, etc., or combinations thereof. Depending on the particular application desired, one may combine a large proportion of alkylene oxide, particularly ethylene oxide, propylene oxide, a combination or alternate additions of propylene oxide and ethylene oxide, or smaller proportions thereof in relation to polyethyleneimine. Thus, the molar ratio of alkylene oxide to polyethyleneimine can range within wide limits, for example, from a 1:1 mole ratio to a ratio of 1000: 1, or higher, but preferably 1 to 200. For

example, in demulsification extremely high alkylene oxide ratios are often advantageously employed such as 200 300 or more moles of alkylene oxide per mole of polyethyleneimine. On the other hand, for certain applications such as corrosion prevention and use as fuel oil additives, lower ratios of alkylene oxides are advantageously employed, i.e., l-10-25 moles of alkylene oxide per mole of polyethyleneimine. With higher molecular weight polyethyleneimine, more oxyalkylatable reaction centers are present for alkylene oxide addition and very high ratios of alkylene oxide can be added. By proper control, desired hydrophilic or hydrophobic properties are imparted to the composition. As is well known, oxyalkylation reactions are conducted under a Wide variety of conditions, at low or high pressures, at low or high temperatures, in the presence or absence of catalyst, solvent, etc. For instance oxy alklation reactions can be carried out at temperatures of from 200 C., and pressures of from 10 to 200 p.s.i., and times of from 15 min. to several days. Preferably oxyalkylation reactions are carried out at 80 to 120 C. and 10 to 30 p.s.i. For conditions of oxyalkylation reactions see U.S. Patent 2,792,369 and other patents mentioned therein.

oxyalkylation is too well known to require a full discussion. For purpose of brevity reference is made to Parts One and Two of U.S. Patent No. 2,792,371, dated May 14, 1 957, to Dickson in which particular attention is directed to the various patents which describe typical oxyalkylation procedure. Furthermore, manufactures of alkylene oxides furnish extensive information as to the use of oxides. For example, see the technical bulletin entitled Ethylene Oxide which has been distributed by the Jefferson Chemical Company, Houston, Tex. Note also the extensive bibliography in this bulletin and the large number of patents which deal with oxyalkylation processes.

The symbol employed to designate oxyalkylation is O. Specifically l-O represents oxyalkylated polyethylcneimine.

In the following oxyalkylations the reaction vessel employed is a stainless steel autoclave equipped with the usual devices for heating and heat control, a stirrer, inlet and outlet means and the like which are conventional in this type of apparatus. The stirrer is operated at a speed of 250 r.p.m. Polyethyleneimine dissolved and/or sus pended in an equal weight of xylene is charged into the reactor. The autoclave is sealed, swept with nitrogen, stirring started immediately and heat applied. The temperature is allowed to rise to approximately C. at which time the addition of the alkylene oxide is started and added continuously at such speed as it is obsorbed by the reaction mixture. When the rate of oxyalkylation slows down appreciably, which generally occurs after about 15 moles of ethylene oxide are added or after about 10 moles of propylene oxide are added, the reaction vessel is opened and an oxyalkylation catalyst is added (in 2 weight percent of the total reactants present). The catalyst employed in the examples is sodium methylate. Thereupon the autoclave is flushed out as before and oxyalkylation completed. In the case of oxybutylation, oxyoctylation, oxystyrenation, and other oxyalkyla-tions, etc, the catalyst is added at the beginning of the operation.

Example 1O Using the oxyalkylation apparatus and procedure stated above, the following compounds are prepared: 900 grams (1 mol) of polyethyleneimine 900 in xylene are charged into a stainless steel autoclave, swept with nitrogen, stirring started, and autoclave sealed. The temperature is allowed to rise approximately 100 C. and ethylene oxide is injected continuously until 220 grams (5 mols) total had been added over a one-half hour period. This reaction is exothermic and requires cooling to avoid a rise in temperature after removal of xylene. The reaction mass is transferred to a suitable container. Upon cooling to room temperature, the reaction mass is a dark extremely viscous liquid.

Example 1-0 The same procedure as Example 1-O is used except that 396 grams of ethylene oxide (9 mols) is added to 900 grams (1 mol) of polyethyleneimine 900. This reaction material is a dark viscous liquid at room temperature.

Example 1-0 The same procedure as Example 1O is used and 396 grams of ethylene oxide (9 mols) are added to 900 grams (1 mol) of polyethyleneimine 900. After this reaction is completed, the autoclave is opened and 20 grams of sodium methylate are added. The autoclave is then flushed again with nitrogen and an additional 572 grams (13 mols) of ethylene oxide is added at 100 C. This reaction is highly exothermic. The reaction mass now contains 1 mol of polyethyleneimine 900 and a total of 22 mols of reacted ethylene oxide.

Example 1-0 A portion of the reaction mass of Example 1-0 is transferred to another autoclave and an additional amount of EtO was added. The reaction mass now contains the ratio of 1 mol of polyethyleneimine 900 to 40 mols of EtO.

Example 1-0 The addition of ethylene oxide to Example lO is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 75 mols of EtO is reached.

Example 1-0 The addition of ethylene oxide to Example 1-0 is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 83 mols of EtO is reached.

Example 1-0 The addition of ethylene oxide to the Example 1-0 is continued until a molar ratio of 1 mol of polyethyleneimine 900 to 105 mols of EtO is reached.

Example 16O 2,000 grams (0.1 mol) of polyethyleneimine of molecular weight of 20,000 in xylene are charged into a con ventional stainless steel autoclave. The temperature is raised to 120 C., the autoclave is flushed with nitrogen and sealed. Then 11.6 grams of propylene oxide (0.2 mol) are added slowly at 120 C. A sample is taken at this point and labeled 16O This sample contains two F mols of P-rO for each mol of polyethyleneimine. It is a dark, pasty solid at room temperature.

Example 16-O The addition of propylene oxide to 16O is continued as follows: The autoclave is opened and 5 grams of sodium methylate are added. The autoclave is again purged with nitrogen and sealed. Propylene oxide is added carefully until an additional 23.2 grams have been reacted. A sample is taken at this point and labeled 16-0 This compound now contains 6 mols of propylene oxide for each mol of polyethyleneimine 20,000.

Example 1 6-0 The oxypropylation of 16O is continued until an additional 52.2 grams of propylene oxide are reacted. A sample is taken at this point and labeled 16-0 16-0 contains mols of propylene oxide for each mol of polyethyleneimine 20,000. At room temperature the product is a dark, pasty solid.

This oxyalkylation is continued to produce examples 16O 16O A summary of oxyalkylated products produced from polyethyleneimines is presented in the following Table II.

The Roman numerals, (I), (II), and (III) besides the moles of oxide added indicate the order of oxide addition (I) first, (II) second and (III) t-hird, etc.

The following abbreviations are also used throughout this application:

EtOEt-hylene oxide PrO-Propylene oxide BuOButylene oxide TABLE II.OXYALKYLATED PRODUCTS Mols of Alkylene Oxide/Moi Polyethyleneimine Physical Ex. Properties EtO PI'O B110 Viscous liquid. Solid.

Do. Viscous liquid.

Do. Solid.

D0. Viscous liquid. Dark, thick mols 12 (III) 5 (I) 10 (II) 5 (III) 0 cidol 4 10 (I) 5 (III) 18 (I) 20 (I) 50 (II) 12 (III) (II) Octyieuc oxide, 8 mols Styrene oxide, 5 mols Epoxide 201 (Carbide dz Carbon) 1 mol 0. Viscous liquid.

Do. Solid.

Viscous liquid.

a s PPP'P'P' oczooooocoo ooooo ocoooooooo ooooo oooocooooo 00000 0. Viscous liquid. Solid.

Do. Viscous liquid.

Do. Do. Solid. Viscous liquid.

TABLE II.-OXYALKYLATED PRODUCTS-Continued TAB LE IPA-Continued Mols of Alkylene Oxide/M01 M015 of Alkylene Oxide Per M01. Wt. Polyethyleneimme Physical Mol. Weight Mol of Polypropyleneunine Ex. of PE Properties E xof Poly- Physical ample D QDY Properties EtO PrO BuO imine EtO PrO BuO 19-05. 36-06.-. 1,000 100 Solid. 19-01. 36-01.-. 1, 000 300 Waxy solid. 19-0 37-01.-. 1, 000 Viscous liquid. 20-01- 37-02.-. 1, 000 D0. 20-02- 10 37-03.-. 1, 000 2o Do. 20-03- 37-04--- 1,000 40 Do. 20-04--. 37-05--. I, 000 80 D0. 20-0 33-01... 1,000 10 (I) 20 (II) Do. 20-Oa--. 3 33-02... 000 (II) 5 (I) Solid 21-0 50, 000 Epichlorohydriu, 3 mols 0. 39-01... 1, 000 4 (I) 3 (II) Viscous liquid, 22-01... 50, 000 (I) 4 (II) 4 (III) Waxy solid. 39-02.-. 1. 000 6 (I) 10 o. 22-01.-. 50, 000 Do. 15 39-03... 1, 000 14 (III) II) Solid. 22-03.-. Do. 39-04... 1,00 10 (II) 10 (III) Thick liquid. 22-04--. Do. 40-0 l, 000 Epoxide 201 (Carbid Solid. 22-0 Do. bon), 2 mols 22-0 Do. 4l-0 1, 000 Styrene oxide, 6 mols Viscous liquid. 23-01-.. Do. 42-0 1, 000 Oetylene oxide, 2 mols Do. 23-01... D0. 43- 1. 000 1 23-03..- Do. 43-02... 5,000 5 23-04... Do. 43-03... 5, 000 20 23-05... Do. 43-0,... 5, 000 45 23-05--. D0. O5-.. 000 75 23-O D0. 43-00--. 5, 000 125 D0. 23-0 Do. -01... 000 Viscous liquid. 24-01--. Do. 44-02-.- 5, 000 12 Thick liquid. 24-02... Do. 44-03... 5, 000 35 Do. 24-03..- D0. 44-04-.. 24-04--- D0. 5" 24-0 Do. 44-06-.- 24-00... 100,000 Do. 44-01... 24-07--. 100,000 D0. 24 0s 100, 000 Do. 40 24-09--. 100, 000 D0. 40-03"- 24O1u-. 100, 000 Do. 45-04-.. 25-01--. 100, 000 D0. 46-01"- 25-0 100, 000 3 (I) Do. 40-02..- 25-0 100, 000 5 (II) Do. 46-Oa-" 25-04--. 100, 000 6 (II) D0. 46-04... 26-01--. 100, 000 8 (III D0. 46-05... 26-0 100, 000 6 (III) D0. 46-06- 26-0 100, 000 5 (II) DO. 26-04--. 100,000 15 (II) D0. 48-01"- 26-0 100, 000 2 (I) Do. 48-02... D 26-Oa--. 100, 000 4 (I) DO. 48-03-.. 48-04... 48- 5 D0. 49-01-.. 49-02..- 000 D The following table presents specific illustration of 1&8?" 888 g8 3gcornpounds other than polyethyleneunme and 1ts denva- 50-01--. 10, 000 1 Do. fives 50-02... 10, 000 D0. 50-0 D0. 51-0 D0. 51-02". DO. TABLE II-A.-OXYALKYLATED PRODUCTS 0F POLY 51-03... Do. PROPYLENEIMINE 51-O D0. 52-0 10, 000 Ootylene oxide, 4 mols D0. 53-O 10,000 Epoxide 201 (Carbide & Oar- D0. Mols of Alkylene Oxide Per ban), 1 mol M01. Weight M01 of Polypropyleneimine 54-01... Waxy solid. Exof Poly- Physicel 54-0 D0. ample propylene- Properties 54-0 Do. imine EtO PrO BuO 54-04- Do. 54-0 Do. 55-01. D0. 27-01... Viscous liquid. 55-0 Do. 27-02... Do. 55-03- Do. 27-03... Solid. 55-0 Do. 27-04--. D0. 55-0 D0. 27-05... DO- 55-013- D0. 27-06... Do. 55 56-0 Do. 28-0 Viscous liquid. 56-0 Do. 28-0 D0. 56-0 D0. 28-03... DO. 56-04 DO. 28-04... 0. 56-05- Do. 28-05... DO. 56-0e D0. 28-05.-. Do. 57-01. D0. 28-07.-. D0. 57-02. D0. 29-0...- Do. 57-03. Do. 29-02.-. Do. 57-04- D0. 29-03 DO. 58-01 D0. 29-0 D0. 58-0 D0. 29 0 D0. 58-0 Do. 30-0, Do. 58-0 Do. 3 0 Paste. 59-01. Do. 31-0 oIid. 5 59-0 Do. 31-0, Thick dark 59-0 Do. quid. 59-04- Do. 32-0 D0. 59- Do. 32-02... D0. 60-01. D0. 32-03... Do. 60-02. Do. 32-0 Do. 60-0 Do. 0 Do. 60-04-. Do. 34-0 500 Styrene oxide, 3 mols Do. 61-01. Do. 35-0 500 Epoxide 201 (Carbide & (331- Solid. 61-02- Do. hon), 1 mo 61-0 Do. 36-0 1, 000 1 61-04. D0. 36-02.-- 1, 000 3 62-01- Do. ss-o m 1,000 12 62-02. D 36-04--. 1, 000 18 36-05..- 1, 000 50 15 ACYLATION THEN OXYALKYLATION Prior acylated polyethyleneimine can be oxyalkylated in the above manner by starting with acylated polyethyleneimine instead of the unreacted polymer. Non-limiting examples are presented in the following tables. The symbol employed to designate an acylated, oxyalkylated polyethyleneimine is A0. Specifically 1A O represents acylated, then oxyalkylated polyethyleneimine.

Example 1-A O For this example an autoclave equipped to handle alkylene oxides is necessary. 1671 grams (1 mole)-of 1A are charged. into the autoclave. Following a nitrogen purge and the addition of 75 grams of sodium methylate, the temperature is raised to 135 C. and 2436 grams of PrO (42 mols) are added. At the completion of this reaction, 440 grams of EtO mols) are added and the reaction allowed to go to completion. The resulting polymer is a dark viscous fluid soluble in an aromatic solvent. Ratio of reactants 1 mole starting material/PrO 42 mols/EtO 10 mols.

Example 2-A O For this example a conventional autoclave equipped to handle alkylene oxides is necessary. 525 grams of 2A (0.1 mol) are charged into the autoclave. The charge is catalyzed with 20 grams of sodium methylate, purged with nitrogen and heated to 150 C. 24.6 grams (0.2 mole) of styrene oxide are added and reacted for four hours with agitation. The resulting product is a dark extremely viscous fluid. Ratio of reactants 1 mole starting material/ 2 moles EtO.

These reactions and other reactions are summarized in the following table.

TABLE III.OXYALKYLATED, PRIOR ACYLATED POLYETHYLENEIMINE [Mols of oxide per mol of reactant] Example EtO PrO BuO Physical Property Viscous liquid.

Do. Dark, viscous liquid. Solid. Thick liquid.

Solid.

Viscous liquid.

Do. Do.

Solid.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IIIA.OXYALKYLATED, PRIOR ACYLATED POLYPROPYLENEIMINE Example EtO PrO BuO Physical Properties IS-A201 10 Viscous liquid. -Az0z 3 D0. 15-11203 (I) 2 (11) Do. 15-11204 6 (II) 10 (III) Do. 15-Az05 DO. 16-A1O Epoxide 201 (Car Do.

Carbon), 1 mol 10 (II) 80 (I) Do. Do.

3 Pasty solid. Oetyleue oxide, 0 mols Do. (II) 5(1) Do. Do. Styrene oxide, rn'ils Do. 5 (III) 1 (II) 2 (I) Do. 12 (II) 65 (I) Do. Epiehlorohydrin, 2 mols D0. 1 Do. 3 i Do.

OXYALKYLATION THEN ACYLATION The prior oxyalkylated polyethyleneimine can be acylated with any of the acylation agents herein disclosed (in contrast to acylation prior to oxyalkylation). Since these reactants also have hydroxy groups, acylation, in addition to reaction with amino groups noted above, also in-' cludes esterification.

The method of acylation in this instance is similar to that carried out with polyethyleneimine itself, i.e., dehydration wherein the removal of water is a test of .the completion of the reaction.

Example 1O A One mole of 1-0 (1120 grams) in 500 ml. of xylene is mixed with three moles of acetic acid (180 grams) at room temperature. The temperature is raised. slowly to -130 C. and refluxed gently for one hour. The temperature is then raised to 150160 C. and heated until 3 moles of water and all of the xylene are stripped off. The dark product is water-soluble.

Example 2O A 0.1 mole of 2-O (380 grams) in 400 ml. of xylene is mixed with 0.1 mole of palmitic acid (25.6 grams) at room temperature. Ratio 1 mole 2-0.; to 1 mole of pal-mitic acid. Vacuum is applied and the temperature is raised slowly until one mole of water (18 grams) is removed. This product is a dark viscous liquid.

Example 2-O A 0.1 mole of 2O (757 grams) is mixed with 500 grams of xylene and heated to 100 C. 0.1 mole of diglycolic acid (13.4 grams) is added slowly to prevent excessive foaming. Ratio 1 mole 2-0 to 1 mole gly-colic acid. The temperature is raised to -150 C. and held until one mole of water has evolved. This product is the diglycolic acid fractional ester of 2O A white precipitate forms during this reaction which can be removed by filtration. Analysis shows the precipitate to be sodium acid diglycollate, a reaction product of the catalyst and diglycolic acid. The filtered product is a dark viscous liquid at room temperature.

Table IV contains examples which further illustrate the invention. The symbol employed to designate oxyalkyl- :ated, acylated products is OA.

TABLE IV.ACYLATED, PRIOR OXYALKYLATED P OLY- E II-IYLENEIMINE Ratio Mols of Mols of Acyl- Water Re- Ex- Acylatlng ating Agent moved to Mols Physical ample Agent Per M01 Oxy- Acylating Properties alkylated PE Agent Employed 1OlA| Acetic 3 1 Dark viscous liquid. 1-01Az.-. Laur1c 1 1 D0. Acetic. 2 1 Solid. 3 1 Do. 1 1 Do. 1 1 Do. 2 1 Do. 6O1A 1 Viscous liquid 12-0 11. 2 1 Do. 13-OaA 1 1 Do. 14O@A 2 I Do. 15-O3A-.. Tall oil 1 1 Do. 16O A 1 1 Do. l7OaA 1 2 Do. 1805A 2 1 D0. 19-O1A 1 1 D0. 20-0 11, Maleic an- 1 Do.

hydride. 22-O5A Linoleic 3 1 Do. 23-0 11.-. Palmitie 1 1 D0. 240 A Acetic 1 1 Do 25-O A1 Dimerie 1 1 Solid (Emery Indus). 25-O A Diglycolicutn l 1 Do. 2fiO A Dipl1eno1ic. 1 1 D0. 26O5A Terephthalid. 1 1 Do. 26-0621. Benzoic 1 1 Do.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE IV-A.ACYLATED, PRIOR OXYALKYLATED POLYPROPYLENEIMINE Mols of Acyl- Ratio Mols oi ating Agent of water Aeylating Per Mol of Removed to Physical Example Agent oxyalkylated Mols of Properties Polypropyl- Aeylating eneimine Agent Employed 27-O2A... Oleic 2 2 Thick dark liquid. 27-O4A... Diphenolic.-. 1 1 Pasty solid. 28-O3A... Laurie 3 1 o. 28-O A-.. Acetic 4 1 Do. 29-02A... Naphthenie 1 1 Do. 31-OzA... Stearic 2 2 D0. 32-O4A... Tall oil. 1 1 Do. 3701A Maleic anhy- 1 Do.

dride. 39-O2A-.. Palmitic 2 2' D0. 43-00A-.. Dimeric 3 1 Waxy solid.

(Emery %n du)sries 44-O A... Diglyeolic 1 1 Pasty solid. 45-O1A..- Myristic 2 1 Do. 48-03A-.. Ricinoleic 1 1 Do. 50-O2A Abietic" 2 2 Do. 51-O4A... Linoleic. 1 1 Do. 57-O3A-.. Nonanoie 1 1 D0. 59-0511-.. Laurie 1 1 Waxy solid. 62-OzA-.. Diglycolic 1 1 D0.

HEAT TREATMENT OF OXYALKYLATED PRODUCTS The oxyalkylated products described herein, for example, those shown in Table II relating to oxyalkylated polyethyleneimine and those in Table III relating to oxyalkylated, prior acylated, polyethyleneimine can be heat treated to form useful compositions.

In general, the heat treatment is carried out at 200- 250 C. Under dehydrating conditions, Where reduced pressure and a fast flow of nitrogen is used, lower temperatures can be employed, for example ISO-200 C.

Water is removed during the reaction, such as by means of a side trap. Nitrogen passing through the reaction mixture and/ or reduced pressure can be used to facilitate water removal.

The exact compositions cannot be depicted by the usual chemical formulas for the reason that the structures are subject to a wide variation.

The heat treatment is believed to result in the polymerization of these compounds and is effected by heating same at elevated temperatures, generally in the neighborhood of ZOO-270 C., preferably in the presence of catalysts, such as sodium hydroxide, potassium hydroxide, sodium ethylate, sodium glycerate, or catalysts of the kind commonly employed in the manufacture of superglycerinated fats, calcium chloride, iron and the like. The proportion of catalyst employed may vary from slightly 18 less than 0.1%, in some instances, to over 1% in other instances.

Conditions must be such as to permit the removal of water formed during the process. At times the process can be conducted most readily by permitting part of the volatile constituents to distill, and subsequently subjecting the vapors to condensation. The condensed volatile distillate usually contains water formed by reaction. The water can be separated from such condensed distillate by any suitable means, for instance, distilling with xylene, so as to carry over the water, and subsequently removing the xylene. The dried condensate is then returned to the reaction chamber for further use. In some instances, condensation can best be conducted in the presence of a high-boiling solvent, Which is permitted to distill in such a manner as to remove the water of reaction. In any event, the speed of reaction and the character of the polymerized product depend not only upon the original reactants themselves, but also on the nature and amount of catalyst employed, on the temperature employed, the time of reaction, and the speed of water removal, i.e., the effectiveness with which the water of reaction is removed from the combining mass. Polymerization can be effected without the use of catalysts in some instances, but such procedure is generally undesirable, due to the fact that the reaction takes a prolonged period of time, and usually a significantly higher temperature. The use of catalyst such as iron, etc. fosters the reaction.

The following examples are presented to illustrate heat treatment. The symbol used to designate a heat treated oxyalkylated polyethyleneimine is OH and an acylated, oxyalkylated product is AOH. In all examples 500 grams of starting material are employed.

Example 2O H A conventional glass resin vessel equipped with a stirrer and water trap is used. Five hundred grams of 2-0 are charged into the above resin vessel along with five grams of CaCl The temperature is raised to 225250 C. and heated until 57 grams of water (3.2 mols) are evolved. This process takes 7.5 hours of heating. The

product is an extremely viscous material at room temperature. However, upon warming slightly this product dissolves easily in water.

The process of the immediately previous example is repeated using 19-0 but substituting sodium methylate for calcium chloride. The product is a dark, viscous, water-soluble material.

Example 15-O H The process of Example 2-O H is repeated using 15-0 but substituting powdered iron for calcium chloride.

TABLE V.HEAT TREATED (I) OXYALKYLATED ANDlg2) ACYLATED, OXYALKYLATED Example Reaction Temp., C.

POLYE'IHYLENEIMIN Water Removed Catalyst (5 grams) Time in Physical Properties Hours Grams Mols 74 4. 1 8.0 Dark, viscous liquid. 57 3. 2 16. 5 Do. 36 2.0 23 Do. 38 2. 1 D0. 95 5. 3 9. 5 Solid. 32 1. 8 12 Viscous liquid. 2. 2 13 D0. 72 4 18 Do. 54 3 24 D0. 5 30 Do. 54 3 16 Do. 36 2 18 D0. 76 4. 2 20 Solid. 54 3 16 Viscous liquid. 63 3. 5 8 Do. 57 3. 2 12 Do. 36 2 14 Do. 38 2. 1 11 D0. 40 2. 2 13 D0. 36 2. 0 16 Paste. 40 2. 2 8 DO. 90 5 14 D0. 32 1. 8 18 D0.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

amines, alkali or alkaline earth metal hydroxides, and the like.

TABLE V-A.HEAT TREATED (1) OPXYALKYLATED AND (2) ACYLATED, OXYALKYLATED OLYPROPYLENEIMINE Water Removed Example Reaction Catalyst (5 grams) Time in Physical Properties Temp, C. Hours Grams Mols 32 1.8 18 Dark, viscous liquid. 40 2. 2 8 D0. 40 2. 2 13 D0. 36 2.0 14 Do. 63 3. 5 8 Do. 76 4. 2 Do. 54 3.0 16 Do. 54 3.0 24 Pasty. 40 2. 2 13 Viscous liquid. 95 5. 3 9. 5 D0. 255 Ferric Chloride 36 2.0 23 Do. 270 "on 74 4. 1 8.0 Do. 225 Aluminum Chloride 32 1. 8 18 Do. 250 CaClz 90 5.0 14 D0. 235 Sodium Methylate 36 2.0 16 Do. Ir 38 2.1 11 Do.

57 3. 2 12 Paste. 54 3.0 16 D0. 36 2.0 18 D0. 90 5.0 Do. 20A10aH... 32 1.8 12 D0.

ALKYLATION Alkylation relates to the reaction of polyethyleneimine and derivatives thereof with alkylating agents.

Any hydrocarbon halide, e.g., alkyl, alkenyl, cycloalkenyl, aralkyl, etc., halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule can be employed to alkylate the products of this invention. It is especially preferred to use alkyl halides having between about one to about eighteen carbon atoms per molecule. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. In practice, the alkyl bromides and chlorides are used, due to their greater commercial availability. Non-limiting examples of the alkyl halide reactant are methyl chloride; ethyl chloride; propyl chloride; n-butyl chloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide; isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride; 2- ethyl-hexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7-ethyl-2-methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride; and triacontyl chloride. In addition, alkenyl halides can also be employed, for example, the alkenyl halides corresponding to the above examples. In addition, the halide may contain other elements besides carbon and hydrogen as, for example, where dichloroethylether is employed.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixtures of alkyl halides, having carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples of such mixtures are mono-chlorinated wax and mono-chlorinated kerosene. Complete instructions for the preparation of mono-chlorowax have been set forth in United States Patent 2,238,790.

Since the reaction between the alkyl-halide reactant and polyethyleneimine is a condensation reaction, or an alkylation reaction, characterized by the elimination of hydrogen halide, the general conditions for such reactions are applicable herein. For certain uses it is preferable to carry out the reaction at temperatures of between about 100 and about 250 C., preferably between about 140 C. and about 200 C., in the presence of a basic material which is capable of reacting with the hydrogen halide to remove it. Such basic materials are, for example, sodium bicarbonate, sodium carbonate, pyridine, tertiary alkyl It is preferred to perform the reaction between the alkyl halide reactant and polyethyleneimine in a hydrocarbon solvent under reflux conditions. The aromatic hydrocarbon solvents of the benzene series are especially preferable. Non-limiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and on the reaction temperature selected. For example, it will be apparent that the amount of solvent used can be so great that the reaction temperature is lowered thereby.

The time of reaction between the alkyl halide reactant and polyethyleneimine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the hydrogen halide from the reaction mixture. In practice, the reaction is continued until no more hydrogen halide is formed. In general, the time of reaction will vary widely, such as between about four and about ten hours.

It can be postulated that the reaction between the alkyl halide reactant and polyethyleneimine results in the formation of products where the alkyl group of the alkylhalide has replaced a hydrogen atom attached to a nitrogen atom. It is also conceivable that alkylation of an alkylene group of polyethyleneimine can occur. However, the exact composition of any given reaction product cannot be predicted. For example, when two moles of butyl bromide are reacted with one mole of polyethyleneimine 900, a mixture of mono-, diand tri and higher N- alkylated products can be produced. Likewise, the alkyl groups can be substituted on different nitrogen atoms in different molecules of polyethyleneimine.

Thus, the term Alkylation as employed here and in the claims include alkenylation, cycloalkenylation, aralkylation, etc., and other hydrocarbonylation as well as alkylation itself.

In general, the following examples are prepared by reacting the alkyl halide with the polyethyleneimine at the desired ratio in the presence of one eqiuvalent of base for each equivalent HCl given off during the reaction. Water formed during the reaction is removed by distillation. Where the presence of the anions, such as chlorine, bromine, etc., is not material and salts and quaternary compounds are desired, no base is added.

The following examples are presented to illustrate alkylation of polyethyleneimine.

In these examples, the term mesomer is employed. A mesomer is defined as a repeating radical which, when combined with other mesomers, forms the principal portion of the polymer molecule.

Thus, the unit 1 I H CC-N is the mesomer of polyethyleneimine, since polyethyleneimine maybe represented by the formula 430 grams of polyethyleneimine 50,000, equivalent to 10 mesomeric units of ethyleneirnine, in 500 ml. of xylene and 570 grams of sodium carbonate, equivalent to 8 moles, are placed in a reaction vessel equipped with a mechanical stirrer, a thermometer and a reflux condenser take-off for removal of volatile components. The stirred reactants are heated to about 100 C. whereupon 1140 g. (8 mols) of dichloroethyl ether is started in slowly at such a rate that the temperature of the reaction vessel contents never exceeds 165 C., but preferably stays around 135 C. The reaction is exothermic and 5-6 hours are required to add all the dichloroethyl ether. After all the dichloroethyl ether has been added, the temperature is allowed to drop to about 90-100 whereupon reduced pressure is applied to the reaction vessel and all xylene stripped out. The material left in the vessel is a thick brown liquid which solidifies upon cooling to a glassy-solid.

Example 8-A The equivalent of 8 mesomeric units, based on polyethyleneimine, of the material 8A (Table 1) in 300 g. xylene is placed in a reaction vessel described in the above example for 5K 340 grams anhydrous sodium carbonate, equivalent to 3.2 moles are added followed by 1.6 moles dimethyl sulfate. The temperature is then brought up to 125 C. and held there for a period of 6-8 hours. Xylene is then removed under reduced temperature and pressure conditions as in the example for 5K The resulting product, a dark amber material, is very viscous at ordinary temperature.

Example 20-O HK The equivalent of 10 mesomeric units based on polyethyleneimine of the material 20O H (Table V) in 300 ml. of xylene and 420 grams sodium bicarbonate, equivalent to 5 moles, are placed in an autoclave equipped with a stirring device, a thermometer and a condenser reflux device which can be closed oil? from the autoclave during reactions in which pressures above atmosphere are experienced. The autoclave is closed and heat is applied to bring up the temperature to 12-0-130 C. at which time 5 moles methyl chloride are added slowly while never allowing pressure to exceed 5 atmospheres pressure. Several hours will be necessary to get all methyl chloride in and pressure inside the vessel down to one atmosphere. At this point the reflux condenser is opened, the temperature is allowed to drop to 90l00 C. and a slight vacuum applied in order to reflux the xylene out of the autoclave. The resulting material is a very viscous amber colored liquid.

The reactions shown in the following table are carried out in a similar manner. Each reaction in the table is carried out in two way(1) in the presence of base, as in 5-K to yield the alkylation product and (2) in the absence of base to yield the halogen-containing or sulfatecontaining (5K X) products.

The alkylated products of this invention contain primary, secondary, tertiary, and quaternary amino groups. By controlling the amount of alkylation agent employed and the conditions of the reaction, etc., one can control the type and amount of alkylation.

For example, by

reaction less than the stoichiometric amount of alkylation agent one could preserve the presence of nitrogen-bonded hydrogen present on the molecule and by exhaustive alkylation in the presence of sufiicient basic material, one can form more highly alkylated compounds.

The moles of alkylating agent reacted with polyethyleneimine will depend on the number of alkylation reactive positions contained therein as well as the number of moles of alkylating agent one wishes to incorporate into the molecule. Theoretically, every hydrogen bonded to a nitrogen atom can be alkylated. We have advantageously reacted 1-20 moles of alkylating agent per moles of polyethyleneimine 900 but preferably 1-12. moles. With polyethyleneimine 20,000 greater amounts of alkylating agent can be employed, for example 1-50 moles, and with polyethyleneimine 40,000, 1-100 moles, etc. Optimum alkylation will depend on the particular application.

In addition, the alkyl halide may contain functional groups. For example, chloroacetic acid can be reacted with polyethyleneimine to yield a compound containing carboxy-lic acid groups PNCH COOH, wherein P is the residue of polyethyleneimine.

In addition, polyethyleneimine can be alkylated with an alkyl halide such as alkyl chloride and then reacted with chloroacetic acid to yield an alkylated polyethyleneimine containing carboxylic acid groups The symbol employed to designate an alkylated polyethylcneimine is K. Where the product is a salt or a quaternary the symbol is KX. Thus, for example, where no acceptor base is employed and a salt is allowed to form 1-A O K would be 1A O KX.

TAB LE VL-ALK YL ATE D P RO D UC TS Mols M01. Wt. Alkylatiug Physical Ex. PE Alkylating Agent Agent Per Propertie Mesomer Unit Allyl chloride. 0. 2 Viscous liquid. do -4. 0.7 Do. Benzyl chloride. 0. 3 Do. do 0.8 Solid.

Methyl chloride. 0. 3 Viscous liquid. do 1.0 Solid.

Ethylene dichlo- 0.2 Viscous ride. liquid. do 0. 5 0. 0 1,4-dichlorobu- 0.2 Do.

tene-2. do 0.5 Do. Dimethyl sulfate 0.2 Do. do 0.4 Do. Dodecylbenzene 0. 2 Solid chloride. do 0.5 Do.

Butyl chloride- 0. 3 Viscous liquid. do 0.6 Do. Dichlorodiethyl 0. 2 Do.

ether. do 0. 8 Solid.

Benzyl chloride. 0.3 Viscous liquid. do 0.8 Solid.

Ethylene dichlo- 0.2 Viscous ride. liquid. do 0.8 Do. Methyl chloride. 0. 3 Do. do 1.0 Solid.

1,4 xylidene chlr 0. 2 Viscous ride. liquid. do 0.2 Do. Dodecenyl chlo- 0.2 Solid.

ride. Methyl chloride. 0. 5 Viscous liquid. Benzyl chloride- 0. 4 Solid. Dimethyl sulfate. 0.2 Viscous liquid. Dichlorodiethyl 0. 4 Do.

ether. 1,4-dichlorobu- 0. 3 Do.

tene-2. B enzyl chloride. 0. 4 Solid. Methyl chloride. 0. 7 D0. Ethylene diehlo- 0.2 Viscous ride. liquid.

TAB LE VI.ALKYLATE D P ROD UCTSC ontinued Mols M01. Wt. Alkylating Physical Ex. PE Alkylating Agent Agent Per Properties Mesomer Unit 6-0 2K Benzyl chloride. 0. 4 Solid. 11-0zK. Dimethyl sulfate.. 0.2 Viscous liquid 14O1K. Dichlorodiethyl 0. 4 Solid.

ether. 16-O4K--- Methyl chloride.-- 0.6 Do. 19-0 2K. Dodecyl benzyl 0. 2 D0.

chloride. 19-O4K- 1,4 xylylene 0. 2 Viscous dichloride. liqu' 20O1K. Benzyl chloride. 0.5 Solid. 22-O K. Methyl chloride. 0. 6 Do. 23-O K Dodecenyl 0.2 Do.

chloride. 24-O4K. Ethylene dichlo- 0. 3 Viscous ride. liquid. 1A O1K... 1,4 dichlorobu- 0.2 Do.

tone-2. 1A5O5K... Benzyl chloride.-. 0.4 Solid. 5A OK.. Dichlorodiethyl O. 4 Do.

ether. 12AzOzK.. Methyl chloride-.. 0. 5 Do. l-OrArK-.. Octadecyl 0. 2 Do.

chloride 2OtAK.... Benzyl chloride..- 0. 4 Do. 14-06AK Dichlorodiethyl 0. 3 Viscous ether. liquid. 22-0 AK... Methyl chloride.-- 0. 6 Do. Benzyl chloride... 0. 6 Solid. .....do 0.4 Do.

Dichlorodiethyl 0. 2 Viscous ether. liquid. Ethylene dichlo- 0. 2 Do.

ride. O1HK. Methyl chloride. 0. 5 D0. 25-OzHK. Dimethyl suliate 0.2 Do.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

TABLE VIA.ACYLATED PRODUCTS Molecular Mols of Weight of Alkylating Physical Example Polypro- Alkylating Agent Agent Per Properties pylene- Mesorner imine Unit 500 Allyl chloride..... 0. 2 Viscous liquid: 500 ....do 0.7 Do. 500 Benzyl chloride. 0.3 Do. 500 .-...do O. 8 Do. 1,000 Methyl chloride... 0. 7 Do. 1,000 .do 1.0 Do. 1,000 Ethylene di- 0. 2 Do.

chloride. 1,000 -do 0.5 Do. 5,000 1-4-chlorobutene-2. 0. 2 Do. 5,000 .--..do 0.5 Do. 5,000 Dimethyl sulfate.. 0. 2 Do. 5,000 .....do 0.4 Do. 10,000 Dodecylbenzene 0. 2 Solid.

chloride. 10,000 ..do 0.5 Do. 10, 000 Butyl chloride.... 0. 3 Do. 10,000 .-...do 0. 6 Do. 20, 000 Dichlorodiethyl 0. 2 Do.

ether. 20,000 .-...do 0.8 Do. 20,000 Bcnzylchloride 0.3 D9. 20,00 0.8 Do. 40, 000 Methyl chloride..- 0. 3 Do. 40, 000 .....do 0. 3 Do. 40,000 Allyl ohloride. 0. 5 Do. Dimethyl sulfate.. 0. 8 Viscous liquid Methyl chloride..- 0.3 Do. Etgylene dichlor- 0.8 Do.

1 e. Dichlorodiethyl 0. 2 Solid.

ether. Benzyl chloride... 0.6 Do. l i-dichlorobutene- 0.3 Do.

Dodecenyl chlor- 0. 5 Viscous ide. liquid. Benzyl chloride... 0. 2 Do. 1,4 xylylene di- 1. 0 Do.

chloride. Dodecyl benzene 0. 8 Do.

chloride. Dimethyl sulfate-. 0.3 Solid. Ethylene di- 0. 7 Do.

chloride.

TABLE VIA.AOYLATED PRODUCTSOontinucd Molecular Mols of I Weight of Alkylating Physical Example Polypro- Alkylating Agent; Agent Per Properties pylene- Mesomer imine Unit 51-OzK Butyl chloride. 0. 2 Solid.

55-03K Allyl chloride... 0. 5 Do.

til-01K Benzyl chloride. 0. 3 Viscous liquid l5 A2O4K..-- Methyl chloride.-- 1. 0 Solid.

19-AaO1K Etldiylcne dichlor- 0.6 Do.

e. 19A3O3K-. Diehloro pentane. 0. 5 Do. 27-O2AK. Diohlorodiethyl 0. 2 Do.

ether.

44-O5AK. Dimethyl sulfate. 1. 0 Do.

51-O4AK.- Methyl chloride. 0. 8 Do.

46-O3HK. Allyl chloride..... 0. 5 Do.

20-A1O2H K. Butyl chloride. 0.2 Do.

In addition to the above examples wherein a base acceptor is employed to remove the acid anion such as halogen, sulfate, etc., the above examples are also prepared omitting the inorganic base from the reaction medium. When this is done, a halogen containing salt, quaternary, etc. is formed. Examples where such salts are formed will be designated as above except that they will contain an X designation for example instead of 1-O A K they will be 1-O A KX, and instead of 22-O AK they will be 22O AKX, etc. X indicates salt formation.

ALKYLATED THEN ACYLATION The alkylated material prepared above can be further treated with acylating agent where residual acylatable amino groups are still present on the molecule. The acylation procedure is essential-1y that described above wherein carboxylic acids react with the alkylated polyethyleneimine under dehydrating conditions to form amides and cyclic amidines. The product depends on the ratio of moles of water removed for each carboxylic acid group, i.e., 1 mole water/1 mole carboxylic essentially amides; more than 1 mole water/ 1 mole carboxylic acid group, essentially cyclic amidines, such as imidazolines.

Such compounds are illustrated in the following table. The symbol employed to designate alkylated, acylated products is KA and acylated, alkylated, acylated products is AKA.

TABLE VII.ACYLATED, PRIOR ALKYLATED POLY- ETHYLENEIMINE OR DERIVATIVE Ratio Mols M ols of Water Acylating Removed Physical Example Acylating Agent Agent Per Per Mole of Properties Mol PE Reactaut Deriv.

1-K A Laurie 4: 1 1 Viscous liquid 2-K3A....- Oleic 1:1 1.5 Do. 3-K1A- Palmitic 1:1 1 Do. 4-K4A. Dimeric 0. 5:1 1 Solid. 5K1A N onanoic 2:1 1 Viscous liquid. 5KZA.--. Ricinolcic 2:1 1. 8 Do. 5K A. Succinic an- 2:1 1 Do.

hydride alkyl (C12)- 5K4A-.-.. Stearic 1:1 1. 5 Solid. 6-K A Myristie 2: 1 1 Viscous liquid.

2-A4KA Acetic 2:1 1 Do. 6A4KA.... Diglycolic 1:1 1 Do. 2O1KA..- Lauric 2:1 1 Do. 1OZKA..-. Oleic 2:1 1. 3 Do. 1-0 I-IKA Maleic an- 1:1 Solid hydride.

The following table presents specific illustrations of compounds other than polyethyleneimine and its derivatives.

Ratio Mols Mols of of Aeylating Water Physical Example Acylating Agent Per M01 Removed Proper- Agent of Polypro- Per M01 of ties pyleneimine Reactant Derivative 2:1 1 Vilsicousd qui 21 1 Do. 1:1 1 Do. 2:1 1 Do. Oleic 2:1 1.3 Do. Maleie anhy- 1:1 Solid.

dride. Lauric 4:1 1 Viscous liquid. Oleic 1:1 1.5 Do. Palmitic 1:1 1 Do. Dimeric 0. 6 :1 1 D0. fil-OzKA N0nanoic 2:1 1 Do. 15A2O4KA Ricinoleie 2:1 1.8 Do. 19A3O3KA Alkylsuccinic 2:1 Solid.

anhydride 20 ((3-12). 44-O5AKA Stearic 1:1 1 Viscous liquid. 46-OaHKA Myristic 2:1 1 Do. 10-A1O2HKA. Acetic 1:1 1 Do.

Olefination Olefination relates to the reaction of polyethyleneimine and derivatives with olefins.

The compositions of this invention, including polyethyleneimine itself as well as reaction products thereof containing active hydrogens, can be reacted with unsaturated compounds, particular compounds containing activated double bonds, so as to add polyethyleneimine across the double bonds as illustrated herein:

PNH cHi=oH-( ioR- PNoH2oH2( ioR Where the compound contains an additional active hydrogen, other unsaturated molecules can be added to the original molecule for example:

o H PN=(CH2CH2COR)2 Where one or more active hydrogens are present at another reactive site, the following reaction could take place:

The reaction is carried out in the conventional manner such as illustrated, for example, in Synthetic Organic Chemistry, Wagner and Zook (Wiley, 1953) page 673.

Non-limiting examples of unsaturated compounds which can be reacted with the polyamine and derivatives thereof including the following-acrylonitrile, acrylic and methacrylic acids and esters crotonic acid and esters, cinnamic acid and esters, styrene, styrene derivatives and related compounds, butadiene, vinyl ethers, vinyl ketones, maleic esters, vinyl sulfones, etc.

In addition, polyethyleneimine and derivatives thereof containing active hydrogens can be used to prepare telomers of polymer prepared from vinyl monomers.

The following are examples of olefination. The symbol employed to designate olefination is U and alkylation, olefination KU.

Example 1-U The olefination reaction is carried out in the usual glass resin apparatus. Since the reaction is that of a double bond with an active hydrogen, no water is eliminated. The reaction is relatively simple, as shown by the following example:

Change 900 grams of polyethyleneimine 900 in xylene (1 mol) into glass resin apparatus. Care should be taken that the PEI 900 is water-free, to eliminate undesirable side reactions. At room temperature, slowly add 53 grams of acrylonitrile (1 mol). The reaction proceeds smoothly without the aid of a catalyst. Warm gently to 80-1 00" C. and stir for one hour.

Example 6-U To 1,000 grams of polyethyleneimine 100,000 (0.01 mol) in 300 grams of xylene, and 1.24 grams of divinyl sulfone (0.01 mol) at room temperature. This reaction is exothermic and the ambient temperature is employed.

Example 2O KAU Same reactions as Example l-U except that 1 mol of methyl acrylate is substituted for acrylonitrile and 2- O KA is substituted for the polyethyleneimine 900. Part of this product is thereupon saponified with sodium hydroxide to form the fatty amino acid salt. 7

Further examples of the reaction are summarized in the following table:

TAB LE VIIL-OLEFINATIO N Mol. Weight Mols of Example of Polyeth- Olefin Olefin Time Temp.,

yleneimine Per 0.

Mol PE l-U 900 Acrylonitrile 1:1 80-100 1U 900 Methylacrylate 2:1 80-100 1Us 900 3:1 90 2U1 5, 000 2: 1 120 2U2 5,000 Ethyl crotonate. 2:1 125 2U 5, 000 Dioetyl maleate- 2:1 100 3-U1 11, 500 Divinyl sulfone- 1:1 3-U 11, 500 yrene 1 :1 90 3-U 11, 500 Lauryl methacrylate 2:1 135 4U1 20,000 Diviuyl sulfone 1:1 -100 4U2..... 20, 000 Methyl methacrylate. 1:1 80-100 4U3 Acrylonitrile 3:1 80-100 Methylaerylate 3:1 80-100 Acrylouitrile 3:1 80-100 Styrene 3:1 Divinyl sulfone- 1:1 70 Ethyl crotonate 2: 1 125 Dioctyl maleate- 2:1 1 hr Styrene 1:1 1 hr 90 Divinyl sulinnp 1:1 1 hr Methylacrylate 1:1 1 hr"..- 80-100 Divinyl sulione 1:1 1 hr 70 Styrene 3:1 2 hrs 90 Dimethyl Inaleate 1:1 1 hr. 100 Dioctyl maleate 2:1 1 hr 100 Ethyl crotonate 2:1 2 hrs. Divinyl sulfone 1:1 1 hr 70 Styrene 4:1 1 hr 90 TABLE VIII.-OLEFINATIONContinuet1 Mol. Weight Mols of Example of Polyeth- Olefin Olefin Time Temp,

yleneimine Per 0.

M01 PE 19O1U Acrylonitrile 3:1 1 hr. 80-100 20-O1U Mcthylacrylatc 3:1 1 hr. ...a 80-100 22-05U Acrylonitrile 3:1 30 min. 80-100 23O1U Methyl methacrylate 1:1 1 hr 80-100 2 1-0111.- Divinyl sulfonenn 1:1 1 hr 70 1A501U Lauryl methacrylat 2:1 3 hrs. 135 2302AU Divinyl sulfone. 1:1 1 hr. 70 14-01111) Dioctyl maleate 2:1 2 hrs 100 4-K U Ethyl crotonate. 2:1 125 4-K AU Ethyl einnamate. 2:1 120 2-A KAU. Styrene 3:1 90 2O1KA Methylacrylate 2:1 80-100 10 HKAU Acrylonitrile" 1: 1 80-100 illustration of and its deriva- 'E1V6S.

TAB LE VIIIA.OLEFINATION O F POLYP ROI YLENEIMINE Mols of Molecular Olefin Time Example Weight of Olefin Per M01 in Temp,

Polyproof Poly- Hours C.

pylenepropyleneimrne irnme 7U1. 500 Styrene 1:1 1 90 7-Uz. 500 Divinyl sulione. l :1 1 70 7- Us. 500 Acrylonitrile 2:1 1 80-100 8-U1 1,000 Dioctyl maleate 1:1 2 120 8U2-.... 1,000 Metl1ylacrylate. 1:1 1 110 8Ua 1, 000 Ethyl cinnamate 3:1 2 125 9U1 5, 000 Lauryl nietha- 1:1 3 130 crylate. 9-Uz- 5, 000 Ethyl crotonate-.. 1: 1 3 120 9-Ua. 5, 000 Acrylonitrile. 4:1 1 80-100 1OU 10,000 Styrene 2:1 1 9O lO-U2. 10, 000 Divinyl sulione 1 :1 1 80 10-U3- 10, 000 Methylacrylate... 2:1 1 100 11U1 20, 000 Lauryl metha- 1:1 3 110 crylate. 11-Uz.-- 20,000 Styrene 2:1 1 90 11-U 20, 000 Divinyl sulfone. 1 1 l 80 12-U]- 40, 000 Methyl acrylate. 2:1 2 120 12-Uz. 40, 000 Acrylonitrile 3:1 1 80 12-U 40, 000 Dioetyl maleate.-. 1:1 4 110 CARB ONYLATION Carbonylation relates to the reaction of polyethyleneimine and derivatives thereof with aldehydes and ketones.

Where primary amino groups are present on the polyethyleneimine reactants, Schiffs bases can be formed on reaction with carbonyl compounds. For example, where an aldehyde such as salicylaldehyde is reacted with polyethyleneimine 900 in a ratio of 2 moles of aldehyde to 1 mole of PE 900, the following type of compound could be formed:

t t ?=N( OHaCHaN) CHzCHzN=ClJ Lesser molar ratios of aldehyde to polyamine would yield mono-Schifls base such as etc. and other isomeric configurations, such as where the Schiffs base is present on the non-terminal amino group rather than on the terminal amino group, etc.

A wide variety of aldehyde may be employed such as aliphatic, aromatic, cycloaliphatic, heterocyclic, etc., in-

eluding substituted derivatives such as those containing aryloxy, halogen, heterocyclic, amino, nitro, cyano, carboxyl, etc. groups thereof. Non-limiting examples are the following;

Aldehydes Benzaldehyde Z-methylbenzaldehyde 3-methylbenzaldehyde 4-methylbenzaldehyde Z-methoxybenzaldehyde 4-methoxybenzaldehyde a-naphthaldehyde b-naphthaldehyde 4-phenylbenzaldehyde Propionaldehyde n-butyraldehyde Heptaldehyde Aldol 2-hydroxybenzaldehyde 2-hydroxy-6-methylbenzaldehyde 2-hydroxy-3methoxybenzaldehyde 2-4-dihydroxybenzaldehyde 26-dihydroxybenzaldehyde 2-hydroxynaphthaldehyde-1 1hydroxynaphthaldehyde-2 Anthrol-Z-aldehyde-l 2-hydroxyfiuorene-aldehyde-1 4-hydroxydiphenyl-aldehyde-3 3hydroxyphenanthrene-aldehyde-4 13dihydroxy-2-4-dialdehydebenzene 2-hydroxy-5-chlorobenzaldehyde 2hydroxy-S-chlorobenzaldehyde 2-hydroxy-3 S-dibromobenzaldehyde 2-hydroxy-3nitrobenzaldehyde 2-hydroxy-3cyanobenzaldehyde 2-hydroxy-3carboxybenzaldehyde 4-hydroxypyridine-aldehyde-3 4-hydroxyquinoline-aldehyde-3 7hydroxyquinolinealdehyde-S Formaldehyde Glyoxal Glyceraldehyde Schiffs bases are prepared with the polyethyleneirnines of this invention in a conventional manner such as described in Synthetic Organic Chemistry by Wagner and Zook (1953, Wiley) pages 728-9.

Where more extreme conditions are employed, the products may be more complex wherein the carbonyl reactant instead of reacting intramolecularly in the case of a Schiffs base may react intermolecularly so as to act as a bridging means between two or more polyethyleneimine compounds, thus increasing the molecular weight of the polyethyleneimine as schematically shown below in the case where formaldehyde is the carbonyl compound:

In addition to increasing the molecular weight by means of aldehydes, these compounds result in the formation of cyclic compounds. Probably both molecular weight increase and cyclization occur during the reaction.

The following examples illustrate the reaction of carbonyl compounds with polyethyleneimines. The symbol employed to designate carbonylation is C, acylation, carbonylation AC, and alkylation, carbonylation KC.

Example 1-C Charge 900 grams of polyethylene'imine 900 and 900 grams of xylene into a conventional glass resin apparatus fitted with a stirrer, thermometer. and side-arm trap. Raise temperature to 90 C. and slowly add 44 grams of acetaldehyde (1 mol). Hold at this temperature for three hours. Vacuum is then applied until all xylene is stripped 011. The reaction mass is a thick dark liquid which is soluble in water.

Example 5-C Using the same apparatus as above, charge 500 g. (0.1) of polyethyleneimine 5,000. While stirring, add slowly at room temperature 8.2 grams of 37% aqueous formaldehyde (0.1 mol of HCHO). After the reaction has ceased, raise temperature to 100 C. The reaction mass may be stopped at this point. It is a viscous watersoluble material. However, it is possible to continue heating under vacuum until all of the water has been eliminated. Cross-linking occurs with this procedure and care must be taken to prevent insolubilization.

Further examples of this reaction are summarized in the following table:

TABLE IX.--CA RBONYLATION TABLE IXA.CARBONYLATION Molec- Mol ular Ratio Weight of Alde- Temp, Time in 5 Example Polypro- Aldehyde hyde to 0. Hours pyleneolyproimine pyleneimine Benzaldehyde 1:1 110 1 do 2:1 110 1 do 3:1 110 1 Salicylalde- 4: 1 120 1 hyde.

3:1 130 3 do 2:1 130 3 Glyceralde- 3:1 125 4 hyde. Heptalde- 2; 1 125 4 hyde. Furfuralde 1:1 100 2 hyde. Glyoxal 1:1 90 1 Benzaldehyde. 4:1 120 2 Formalde- 1:1 1

hyde. Acetaldehyde- 1:1 100 2 o 2:1 100 2 do 3:1 100 2 Salicylalde- 1:1 130 3 hyde. 51-01110" d 2:1 130 3 32-01110 do 3:1 130 3 AZO1HC Benzaldehyda 3:1 125 2 M01. M01 Ra 8-K4C do 2:1 125 -2 Weight of Aldehyde Temp. 1:1 125 2 Example Polyethyl- Aldehyde toPolyeth- C. Time 2:1 100 1 eneimine ylerigimine 1 1 100 1 or eriv. do 0.5:1 100 1 7-U2 Formalde 2:1 70 1 hyde. 1-C1 900 Aceta1dehyde 1:1 90 3hours. 12-U 0 do 1:1 70 1 22s 2s a- 1- 3 o o. 3-8:

flep y Start at 25 C.,raise to 100 0. z O C 0 33 2,3} The examples presented above are non-limiting ex- 0 g8 g amples. It should be clearly under-stood that various other 5 140 combinations, order of reactions, reaction ratios, multi- M 140 D plicity of additions, etc., can be employed. Where addi- 140 3; tional reactive groups are still present on the molecule, Formaldehyde- (I) 1 hour: the reaction can be repeated with either the original re- 2888 E; E actant or another reactant 0 2 1 0. 100,000 h g 125 5 110mm The type of compound prepared 1s evident from the let- 100000 j il 125 Do, ters assigned to the examples. Thus, taking the branched 1001000 21 125 polyamine as the starting material the following example 2h 100000 3 3 1 120 ours designations have the following meanlng:

5% 2,3, Exanzrzl; disiguation A 1 t d Meaning :1 o. cy a e 5 no 2 A0 Ac lated, then oxyalkylated. 3.1 100 2h011l5 Y 2:1 100 D0 (3) AOA Acylated, then Oxyalkylated, then do 1:1 100 Do.

Formaldehyde 3:1 (2) 1 hour aorylated- 22-050-- do 2:1 (2) Do. (4) AOH Acylated, then Oxyalkylated, then 1-A501C d0 111 (2) D0. heat treated 1-A5OrO Gl ycgralde- 3:1 130 4hours (5) S It t I r f (1) y AX aor uaena o 6A.:OC do 2:1 130 Do. q y 12-0211 Furfuralde- 3:1 100 lhour. AOX Salt of quaternary 0f h d 00 D (7) AOAX Salt or quaternary of (3).

g h 8: 5 (8) AOHX Salt or quaternary of (4). 3:1 140 fihours. (9) O oxyalkylated.

{4.3 B3; (10 0A Oxyalkylated, then acylated. 3:1 (2) l u (11) OH Oxyalkylated, then heat treated. 1 (3 B3; 12 K Alkylated.

7 (13) KX Salt or quaternary of (12).

(14) KA Alkylated, then acylated. (15) AK Acylated, then alkylated. (16) AKX Salt or quarternary of (15). (17) OK Oxyalkylated, then alkylated. (18) OKX Salt or quaternary of (17).

1 Start at 25 (3., raise to 100 C.

2 Start at 25 0., raise to C.

The following table presents specific illustration of compounds other than polyethyleneimine and its derivatives.

31 Example designation Meaning (19) C Carbonylated. (20) AC Acylated, then carbonylated. (21) KC Alkylated, then canbonylated. (22) CO Carbonylated, then oxyalkylated. (23) U Olefinated. (24) AU Acylated, then olefinated. (25) K-U Alkylated, then olefinated. (26) KUX Salt or quaternary of (25).

In addition to polyethylleneimine itself, other polyalkyleneim'ines can be employed, a typical example of which is polypropyleneimines. Propyleneimine is now commercially available and can be polymerized to the polymer and polypropyleneimine can then be reacted in a manner similar to those reactions shown above. Thus, the teachings contained herein also apply to other polya lkyleneimines besides polyethyleneimine and derivatives thereof.

USE AS A CHELATING AGENT This phase of the invention relates to the use of the compounds of our invention as chelating agents and to the chelates thus formed.

Chelation is a term applied to designate cyclic structures arising from the combination of metallic atoms with organic or inorganic molecules or ions. Chelates are very important industrially because one of the unusual features of the chelate ring compounds is their unusual stability in which respect they resemble the aromatic rings of organic chemistry. Because of the great aflinity of chelating compounds for metals and because of the great stability of the chelates they form, they are very important industrially.

The compositions of this invention are excellent chelating agents. They are particularly suitable for forming chelates of great stability with a wide variety of metals.

Chelating metals comprise magnesium, aluminum, arsenic, antimony, chromium, iron, cobalt, nickel, palladium, and platinum. Particularly preferred of such metals as ohe-late constituents are iron, nickel, copper and cobalt.

The chelates formed from the compositions of our invention are useful as bactericidal and fungicidal agents, particularly in the case of the copper chelates. In addition the chelates can be employed to stabilize hydrocarbon oils against the deleterious effects of oxidation.

In general, these chelates are prepared by adding a sufficient amount of a metal salt to combine with a compound of this invention. They are prepared by the general method described in detail by Hunter and Marriott in the Journal of the Chemical Society (London) 1937, 2000, which relates to the formation of chelates from metal ions and salicylidene imines.

The following examples are illustrative of the preparation of chelates.

Example 1-A7 An aqueous 0.1 mole solution of the chelating agent of Example 1-A7 is added to an aqueous solution of 0.02 mole cupric acetate. The solution becomes darker in blue color immediately with the formation of the copper chelate. Inability of the solution to plate out copper on a clean and polished iron strip indicates that the copper is effectively removed from solution by the formation of a chelate.

Example 1-0 An aqueous solution of 0.1 mole of the chelating agent of Example 1-0 is added to an aqueous solution containing 0.025 mole ferrous sulfate. Lack of the usual formation of a red sediment in the water subsequently due to oxidation and precipitation of iron as hydrated oxide shows the iron had been chel-ated while in the ferrous form by the reagent 1-O and thus effectively removed from further reactions.

32 Example 1A O An aqueous solution of 0.1 mole of the chelating agent 1A O is treated with an aqueous solution containing 0.01 mole nickelou s acetate. The solution turns to a darker green indicating that a chelate type of material had been formed.

To avoid repetitive detail, chelates are formed from the above copper, iron and nickel salts and the compounds shown in the following table.

CHELATING AGENTS Polyethyleneimine, molecular wt. 900 Polyethyleneimine, molecular wt. 5,000 Polyethyleneimine, molecular Wt. 11,500 Polyethyleneimine, molecular wt. 20,000 Polyethyleneimine, molecular wt. 50,000 Polyethyleneimine, molecular wt. 100,000

CHELATING AGENTS Polypropyleneimine, molecular weight 500 Polypropyleneimine, molecular Weight 1,000 Polypropyleneimine, molecular Weight 5,000 Polypropyleneimine, molecular weight 10,000 Polypropyleneimine, molecular weight 20,000 Polypropyleneimine, molecular weight 40,000

INHIBITING FOAM This phase of the invention relates to the use of the compositions of our invention in a process for reducing or destroying foam or inhibiting its formation in environments of either an aqueous or a non-aqueous nature.

Foams occur as undesirable, incidental features in many industrial processes. The theory of their formation is not highly developed; so that hypotheses on which foam reduction or destruction processes might be based are difficult to formulate. As a consequence, the effectiveness of foam-destroying agents are difficult to predict.

Our novel process of reducing or destroying foams and of preventing their formation appears to be relatively general in applicability, in that it may be used with compositions comprising aqueous materials or solutions, compositions comprising nonaqueous materials, such as hydrocarbon liquids, and compositions comprising mixtures of aqueous and nonaqueous media. Our process consists in subjecting a foaming or potentially-foaming composition to the action of a small proportion of the reagents of this invention as anti-foamers, thereby causing the foaming properties of the liquid to be diminished, suppressed or destroyed. In applying our process to the reduction or destruction of a foam, the reagent is poured or sprayed or dripped into the body of foam on top the liquid, as desired; and the foam breaks and is destroyed or reduced, substantially at once, as a consequence of such addition of said reagent. Adding the reagent to the liquid underlying such already-formed foam is also practicable. In applying our process to the prevention of foaming, the reagent is admixed, in some small proportion, with a potentially-foaming liquid, by any desired or suitable procedure. The ability of the system to foam is destroyed or at least materially reduced by such addition of said reagent.

It is usually convenient to dilute our reagents during manufacture or before use with some suitable solvent. Solvents generally suitable for incorporation into our reagent include: water; petroleum hydrocarbons, like gaso line, kerosene, stove oil, aromatic solvent; coal tar products, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil; alcohols particularly aliphatic alcohols like methyl, ethyl, isopropyl, butyl, hexyl, octyl, etc. Miscellaneous solvents, such as pipe oil, carbon tetrachloride, etc. may be employed. Sometimes other factors such as whether it imparts an objectionable odor to the defoamed composition or to the products into which it finds its way will determine the choice of solvent. In general, the amount of finished anti-foamer reagent employed is so small that considerable tolerance of undesirable properties in a solvent exists.

The mixture of active ingredient and solvent is stirred until homogeneous. We prefer to employ a petroleum distillate in the proportion of 25 to 30% of the finished product, by volume, although water is an excellent solvent in some instances.

We desire to point out that the superiority of the reagent contemplated by our process is based upon its ability to reduce or destory foam, or to prevent foam formation, in certain foaming or potentially foaming compositions more advantageously and at lower cost than is possible with other reagents or processes. Our reagents are useful in controlling foams in many different types of systems, aqueous and non-aqueous. They will control foams encountered in the manufacture of alkaline hypochlorite bleaches. They are effective in controlling foam in petroleum production and refining operations. They are effective in inhibiting foam in a gas-treating system, in which a mixture of glycols and alkanolamines is used to dehydrate and purify natural gas.

We can apply our reagents to the control of foam in protein adhesives solutions, such as casein and soybean adhesives, as used in the plywood industry, in papermaking, latex adhesives, printing inks, aqueous emulsion paints, which all produce foams which are amenable to our reagents.

In the foregoing description we have made it clear that our reagents may be used to reduce, destroy, or prevent foam. In the appended claims we have used the Word inhibit to include all these corrective and preventive aspects of our process and reagents.

The procedures employed in practicing our process are numerous. The following description will illustrate several techniques commonly employed. It should be understood that the claims are not limited to the procedures described, and that our process consists broadly in bringing into contact by any suitable means our reagent and the foam or the potentially foaming composition.

In controlling foam in a glycol-amine gas treating plant handling natural gas, the glycol-amine mixture has a volume of about 2,000 gallons and make-up is about 2,000 gallons a month. The reagents are injected into the liquid mixture in the return line from the stripping operation, by means of an electrically-powered proportioning pump of conventional design. The feed rate is less than 1 quart daily. Foam difficulties in the system are satisfactorily controlled by this procedure.

In sewage plants, for example, in activated sludgeprocess plants, foam is frequently a serious problem in aeration basins and elsewhere. In one such plant, our reagents will control foam when sprayed into the head of foam, or when sprayed into or simply poured into 34 the liquid in such basins. The foam-inhibiting effect appears to persist quite satisfactorily.

Determination of the optimum or minimum amount of our foam-inhibiting reagents to be used in any application is accomplished in different ways. Small portions of the potentially foaming liquid are added to test bottles, different small proportions of our reagent added, and the chemicalized samples shaken for a short time. Simple observation of the relative speed and completeness of foam destruction should permit selection of the best reagent proportion to be applied on the large scale. The easiest way to determine the amount of reagent required is to introduce it into the foaming or potentially foaming liquid in a fairly large proportion, e.g., 1%, and then to reduce the reagent feed rate until foam destruction is just being accomplished satisfactorily. Usually foam destruction is directly proportional to the amount of reagent used, at least up to about 1% of reagent. In a few instances, it may be found that using more or less reagent than an optimum proportion Will give inferior results.

If the proportions of reagents to be employed in the above test are very small, it may be desirable to determine the optimum proportions of foaming composition and anti-foamer by introducing the latter into the sample of foaming liquid in the form of a solution in a suitable solvent.

Our process is equally applicable to systems in which a foam is already in existence and to systems which are potentially foaming composition, in that they have the property of producing foams when agitated or mixed with air or some other suitable gas. Destruction, reduction and prevention are substantially equivalent actions. It is impossible to determine Whether the reagent does in fact prevent the formation of the initial laminae of foam or whether such initial laminae are destroyed by the reagent before subsequent laminae of sufficient stability to produce a foam can be superimposed thereon. By foaming composition in the appended claims we mean a composition which is either actually foaming or which is capable of producing a foam under suitable conditions, e.g., by simply passing air through it.

In most instances, our reagents are effective to the extent that they destroy an existing foam substantially completely. In some instances, as when too little reagent is used and foam reduction may be slow or even incomplete, we intend that the description and our invention relate both to complete destruction and to partial destruction of foams.

The proportions of our reagent required to be employed appear to vary widely. However, we generally use our reagent in amounts 1% by volume or less of the foaming composition. Usually, the amounts required will be between 0.1% and 0.0001% by volume based on the volume of the foaming composition.

Our present reagents may be used in conjunction with any other effective and compatible anti-foamer. It should also be stated that they are useful in conjunction with foam-inhibiting processes which are mechanical or electrical in character, rather than chemical. For example, some foams may be effectively destroyed by water sprays or jets. Incorporation of a small proportion of our reagents into such water sprays increase their effectiveness. US. Patent No. 2,240,495, to Dillon et al., dated May 6, 1941, relates to a process for resolving foam by means of high electrical potential. Incorporation of a small proportion of our present reagents into the foaming liquid increases the effectiveness of such electrical processes.

The following examples are presented to illustrate our invention.

A foam is effected in a graduated cylinder containing mineral oil'by bubbling nitrogen into the system. At equilibrium the height of the foam is measured and when the nitrogen is shut off, the time for the foam to drop is also measured. This procedure is repeated employing the compounds shown in the following table in ratios of 0.001% by volume in the oil.

The presence of these compounds effectively reduces the height of the foam that is formed and aids in its elimination.

COMPOUNDS USED TO INHIBIT FOAM Polyethyleneimine, molecular wt. 900 Polyethyleneimine, molecular wt. 5,000 Polyethyleneimine, molecular wt. 11,500 Polyethyleneimine, molecular wt. 20,000 Polyethyleneimine, molecular wt. 50,000 Polyethyleneimine, molecular wt. 100,000

COMPOUNDS USED TO INHIBIT FOAM Polypropyleneimine, molecular wt. 500 Polypropyleneimine, molecular wt. 1,000 'Polypropyleneimine, molecular wt. 5,000 Polypropyleneimine, molecular Wt. 10,000 Polypropyleneimine, molecular wt. 20,000 Polypropyleneimine, molecular wt. 40,000

Having thus described our invention, what We claim 40 as new and desire to obtain by Letters Patent is:

1. A process of inhibiting foam which is characterized by subjecting a system susceptible to foaming to the action of a compound selected from the group consisting of (1) a linear polymer of a 1,2-alkyleneimine, said poly- 45 mer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, (2) an acylated linear polymer of a 1,2-alkyleneimine,

(3) an oxyalkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about p.s.i. to about 200 p.s.i., said polymer with an alkylene oxide having at least 2 carbon atoms,

(4) an alkylated linear polymer of a 1,2-alkylene imine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to carbons, formed by reacting, at a temperature of from about 100 C. to about 250 C., said poly-mer with a hydrocarbon halide alkylating agent having 1 to carbon atoms,

(5) an olefinated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular Weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about 70 C. to about 100 C., said polymer with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones,

(6) a Schifi base reaction product of a linear polymer of a 1,2-alkyleneimine, said poly-mer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting said polymer with a compound selected from the group consisting of aldehydes and ketones,

(7) an acylated, then oxyalkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said linear polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer, at a temperature of from about C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., with an alkylene oxide having at a least 2 carbon atoms,

(8) an oxyalkylated, then acylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., said polymer with an alkylene oxide having at least 2 carbon atoms and then reacting said oxyalkylated polymer, at a temperature of from about 120 C. to about 300 C., with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction,

(9) an alkylated, then acylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about C. to about 250 C., said polymer with a hydrocarbon halide alkylating agent having 130 carbon atoms, and then reacting said alkylated polymer, at a temperature of from about C. to about 300 C., with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction,

(10) an acylated, then alkylated linear polymer of a i 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 220 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer, at a temperature of from about 100 C. to about 250 C., with a hydrocarbon halide alkylating agent having 1-30 carbon atoms,

(11) an oxyalkylated, then alkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 220 carbon atoms, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., said polymer with an alkylene oxide having at least 2 carbon atoms, and then reacting said oxyalkylated polymer, at a temperature of from 37 about 100 C. to about 250 C., with a hydrocarbon halide alkylating agent having 1-30 carbon atoms,

(12) a Schifl base reaction product of an acylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular Weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer with a compound selected from the group consisting of aldehydes and ketones,

(13) a Schitf base reaction product of an alkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polymer with a hydrocarbon halide alkylating agent having 1-30 carbon atoms, and then reacting said alkylated polymer with a compound selected from the group consisting of aldehydes and ketones,

(14) an oxyalkylated Schiif base reaction product of a linear polymer of a 1,2-alkyleneimine, said linear polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms formed by reacting said linear polymer with a compound selected from the group consisting of aldehydes and ketones to form said Schitf base reaction product and then reacting said Schiff base reaction product, at a temperature of from about 80 C. to about 200 C. and a pressure of from about p.s.i. to about 200 p.s.i., with an alkylene oxide having at least 2 carbon atoms,

(15) an acylated, then olefinated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said linear polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer, at a temperature of from about 70 C. to about 100 C., with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones, and

(16) an alkylated, then olefinated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2-20 carbon atoms, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polymer with a hydrocarbon halide alkylating agent having from 1-30 carbon atoms, and then reacting said alkylated polymer, at a temperature of from about 70 C. to about 100 C., with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones.

2. The process of claim 1 wherein the compound is a linear polymer of a 1,2-alkyleneimine, said polymer having a molecular Weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms.

3. The process of claim 1 wherein the compound is an acylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about 120 C. to about 300 C., said linear polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction.

4. The process of claim 1 wherein the compound is an oxyalkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about C. to about 200 C. and a pressure of from about 10 psi. to about 200 p.s.i., said polymer with an alkylene oxide having at least 2 carbon atoms.

5. The process of claim 1 wherein the compound is an alkylated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbons, formed by reacting, at a temperature of from about C. to about 250 C., said polymer with a hydrocarbon halide alkylating agent having 1 to 30 carbon atoms.

6. The process of claim 1 wherein the compound is an olefinated linear polymer of a 1,2-alkyleneimine, said polymer having a molecular Weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about 70 C. to about 100 C., said polymer with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones.

7. The process of claim 1 wherein the compound is a Schiif base reaction product of a linear polymer of a 1,2-alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting said polymer with a compound selected from the group consisting of aldehydes and ketones.

8. The process of claim 1 wherein the compound is an acylated, then oxyalkylated linear polymer of a 1,2 alkyleneimine, said polymer having a molecular weight of at least 800, each alkylene unit therein having 2 to 20 carbon atoms, formed by reacting, at a temperature of from about C. to about 300 C., said linear polymer with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polymer, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., with an alkylene oxide having at least 2 carbon atoms.

9. The process of claim 1 wherein the linear polymer of a 1,2-alkyleneimine is polyethyleneimine.

10. The process of claim 2 wherein the linear polymer of a 1,2-alkyleneimine is polyethyleneimine.

11. The process of claim 3 wherein the linear polymer of a 1,2-alkyleneimine is polyethyleneimine.

12. The process of claim 4 wherein the linear polymer of a 1,2-alky1eneimine is polyethyleneimine.

13. The process of claim 5 wherein the linear polymer of a 1,2-alkyleneimine is polyethyleneimine.

14. The process of claim 6 wherein the linear polymer of a 1,2-alkyleneimine is polyethyleneimine.

15. The process of claim 7 wherein the linear polymer of a 1,2-alkyleneimine is polyethyleneimine.

16. The process of claim 8 wherein the linear polymer of a 1,2-alkyleneimine is polyethyleneimine.

17. The process of claim 1 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

18. The process of claim 2 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

19. The process of claim 3 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

20. The process of claim 4 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

21. The process of claim 5 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

22. The process of claim 6 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

39 23. The process of claim 7 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

24. The process of claim 8 wherein the linear polymer of a 1,2-alkyleneimine is polypropyleneimine.

References Cited by the Examiner UNITED STATES PATENTS 40 2,588,343 3/1952 Bird 25232l 2,588,344 3/1952 Bird 25232l 2,598,213 5/1952 Blair 252-392 OTHER REFERENCES SchwartZ-Perry, Surface Active Agents, published by Interscience Publishers, Inc., New York, 1949, page 173.

LEON D. ROSDOL, Primary Examiner.

H. B. GUYNN, Assistant Examiner. 

1. A PROCESS OF INHIBITING FOAM WHICH IS CHARACTERIZED BY SUBJECTING A SYSTEM SUSCEPTIBLE TO FOAMING TO THE ACTION OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) A LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, (2) AN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THERIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120* C. TO ABOUT 300* C., SAID LINEAR POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (3) AN OXYALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 80* C. TO ABOUT 200* C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., SAID POLYMER WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, (4) AN ALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBONS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100* C. TO ABOUT 250* C., SAID POLYMER WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1 TO 30 CARBON ATOMS, (5) AN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THERIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 70* C. TO ABOUT 100* C., SAID POLYMER WITH AN OLEFINATING AGENT SELCTED FROM THE GROUP CONSISTING OF ACRYLOITRILE, STYRENE, BUTADIENE, VINYL ETHERS AND VINYL SULFONES, (6) A SCHIFF BASE REACTION PRODUCT OF A LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2 TO 20 CARBON ATOMS, FORMED BY REACTING SAID POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (7) AN ACYLATED, THEN OXYALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120* C. TO ABOUT 300* C., SAID LINEAR POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 80* C. TO ABOUT 200* C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, (8) AN OXYALKYLATED, THEN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THERIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABUT 80* C. TO ABOUT 200* C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., SAID POLYMER WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS AND THEN REACTING SAID OXYALKYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 120* C. TO ABOUT 300* C., WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (9) AN ALKYLATED, THEN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID OLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100* C. TO ABOUT 250* C., SAID POLYMER WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, AND THEN REACTING SAID ALKYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 120* C. TO ABOUT 300* C., WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (10) AN ACYLATED, THEN ALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120* C. TO ABOUT 300* C., SAID POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTIGN OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 100* C. TO ABOUT 250* C., WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, (11) AN OXYALKYLATED, THEN ALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPEATURE OF FROM ABOUT 80* C. TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., SAID POLYMER WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, AND THEN REACTING SAID OXYALKYLATED POLYMER, AT A TEMPERATUE OF FROM ABOUT 100* C. TO ABOUT 250* C., WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, (12) A SCHIFF BASE REACTION PRODUCT OF AN ACYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120* C. TO ABOUT 300* C., SAID POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBN ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (13) A SCHIFF BASE REACTION PRODUCT OF AN ALKYLATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FORM ABOUT 100* C. TO ABOUT 250* C., SAID POLYMER WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, AND THEN REACTING SAID ALKYLATED POLYMER WITH A COUMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (14) AN OXYALKYLATED SCHIFF BASE REACTIN PRODUCT OF A LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID LINEAR POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THEREIN HAVING 2-20 CARBON ATOMS FORMED BY REACTING SAID LINEAR POLYMER WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES TO FORM SAID SCHIFF BASE REACTION PRODUCT AND THEN REACTING SAID SCHIFF BASE REACTION PRODUCT, AT A TEMPERATURE OF FROM ABOUT 80* C. TO ABOUT 200* C. AND A PRESSURE OF FROM 10 P.S.I. TO ABOUT 200 P.S.I., WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, (15) AN ACYLATED, THEN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT THERIN HAVING 2-20 CARBON ATOMS, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120* C. TO ABOUT 300* C., SAID LINEAR POLYMER WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYMER, AT A TEMPERATURE OF FROM ABOUT 70* C. TO ABOUT 100* C., WITH AN OLEFINATING AGENT SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, STYRENE BUTADIENE, VINYL ETHERS AND VINYL SULFONES, AND (16) AN ALKYLATED, THEN OLEFINATED LINEAR POLYMER OF A 1,2-ALKYLENEIMINE, SAID POLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST 800, EACH ALKYLENE UNIT 